Oxyalkylated omega-methylol-substituted alkylacetophenones



Unit

\ States OXYALKYLATED OMEGA-METHYLOL-SUBSTI- TUTED ALKYLACETOPHENONES No Drawing. Application March 17, 1958 Serial No. 721,651

4 Claims. (Cl. 260-592) This application is a continuation-in-part of my copending application, Serial No. 540,346, filed October 13, 1955, now abandoned.

This invention relates to a novel class of compounds which are particularly etfective as surface active agents, referred to herein as the poly-(oxyalkylene) ethers of certain alkyl aromatic carbinols or the alkyl naphthene analogs thereof. More specifically, this invention concerns surface active agents and detergents formed by oxyalkylation of certain monoand polyhydric alkanols containing a hydrophobic group comprising an alkyl-substituted cyclic hydrocarbon radical and a hydrophilic substituent on the alpha carbon atom of the alkanol chain, as hereinafter more specifically characterized.

Poly-(oxyalkylene) groups, in which the oxyalkylene units are selected-from the oxyethylene and oxypropylene and containing a certain minimum number of such units are recognized in the chemical arts as a convenient source of the hydrophilic radical essential in the structure of surface active products, particularly in the synthesis of Water-soluble compounds having detergent properties. The introduction of a poly-(oxyalkylene) group into compounds containing a hydrophobic radical has, in general, been limited to the alkyl phenols and alkylaryl amines as substantially the only class of starting materials available for this purpose. Because of the limited number of possible phenolic compounds having the requisite structure suitable for the synthesis of surface active agents therefrom, the variety of starting materials available for this purpose is small and few of the products are highly effective surface active agents. Thus, the nuclearly alkylsubstituted phenols in which the alkyl group on the phenolic nucleus contains from about 6 to about 15 carbon atoms have been recognized as a suitable class of starting materials from which surface active agents may be manufactured by condensation of the phenolic hydroxyl group with an oxyalkylating agent, such as ethylene oxide or propylene oxide, the condensation resulting in the formation of a long-chain poly-(oxyalkylene) radi cal which provides the hydrophilic group in the structure of these compouds, requisite to their use as surface active agents. In addition, certain alkyl phenyl-substituted alkanols are also known in the chemical arts as a suitable source of starting materials for the preparation of surface active agents and detergents, but these have generally been limited to the simple monohydric alkanols containing only a single hydroxyl group from which a hydrophilic radical could be fabricated by oxyalkylation. The possible structures available in the class of alkylaryl-substituted monohydric alkanols also places a limitation on the variety of surface active compounds available from this source of starting material. It has now been discovered, and these discoveries form the basis of the present invention, that a group of alkylphenyl-substituted polyhydric alkanols may be synthesized from readily available starting materials of variable and determinable structure and the surface activity of the resulting oxy- Patented Feb. 2, 1961) ice the group consisting of ethylene oxide, glycidol, propylene oxide and mixtures thereof and continuing the oxyalkylation reaction until the resulting product contains from about 6 to about 30 total average number of oxyalkylene units.

Another embodiment of this invention concerns a modification of the foregoing product, further characterized in that the intermediate formed by condensing said alkylacetophenone with formaldehyde is subjected to hydrogenation of suflicient intensity to reduce the carbonyl group of said acetophenone condensation product prior to the oxyalkylation reaction. Still other embodiments of this invention concern the products formed by the reduction of the nuclear aryl group in the structure of the intermediate alkylacetophenone-formaldehyde condensation product.

The products of this invention are characterized structurally as a composition containing an alkyl-substituted cyclic hydrocarbon radical as the hydrophobic portion of the molecule and at least one poly-(oxyalkylene) chain as the hydrophilic radical. One of the ultimate product species of this invention which provides an intermediate for another product species may be represented by the following formula:

wherein Ar is a mono-cyclic hydrocarbon radical selected from polyvalent benzene and polyvalent cyclohexane, R is an alkyl group containing from 6 to about 18 carbon atoms, R' is a methyl group which may be substituted on the phenyl nucleus p times, where p is a whole number having a value of from 0 to 2, Y is a radical selected from the group consisting of hydrogen, methyl, and methylol, n is a number having a value of from 2 to about 10, x is a whole number having a value of from 1 to 3.

Another species of product within the scope of this invention is the series of compounds formed by hydrogenating the carbonyl group of the above product to an hydroxyl radical, followed, if desired, by condensation of the hydroxyl radical with an oxyalkylating agent to yield a product of the following structure:

wherein Ar, R, R, p, m, n and x are identified as indicated in the preceding formula and Y is selected from the group consisting of hydrogen, methyl and methylol. The hydrophobic radical is characterized as a nuclearly alkyl-substituted cyclic hydrocarbon group in which .the cyclic portion of the hydrocarbon is a C ring and contains a single nuclearly-substituted alkyl substituent having from 6 to about 18 carbon atoms. The hydrophilic portion of the molecule which is requisite to its surface active properties is present in the products of this invention in the form of one or more poly-(oxyalkylene) chains linked to an ethyl radical on the cyclic hydrocarbon nucleus through one or more ether oxygen atoms, the poly-(oxyalkylene) radicals being made up of oxy- .ethylene, oxypropylene, and/or oxypropylol units, the

alkylated products resulting from these starting materials total average number of oxyalkylene units per molecule,

whether present in a single poly-(oxyalkylene) chain or multiple poly-(oxyalkylene) chains, is within the range of from about 6 to about 30. These products, in general possess surface activity and when the size and effect of the hydrophobic alkyl cyclic hydrocarbon group is balanced with respect to the hydrophilic poly-(oxyalkylene) chains, the product possesses detergent properties, The term surface active agents as descriptive of the predominant physical properties of the present products is intended to include in specific instances the use of these materials as emulsifying agents, softening agents, wetting agents and other types of products which have the common property of being capable of reducing the surface tension of Water or other solvent in which the product may be dissolved. In certain instances the products are useful as surface active agents and are soluble in Water, while other products in which the hydrophobic portion of the molecule predominates, may be more readily soluble in organic solvents, such as hydrocarbons or alcohols. In each instance, irrespective of the solubility relationship of the product, the latter is characterized by complete neutrality in aqueous solution. All of the above various species of product comprising this invention are non-ionic in solution and accordingly are distinguished from the other types of detergents containing metallic or other ionizable radicals, referred to as ionic surface active agents.

The alkyl cyclic hydrocarbon substituted monohydric or polyhydric alkanols which may be considered as starting materials in the preparation of the present surface active products are most conveniently prepared by synthetic means utilizing an alkyl benzene hydrocarbon as the primary starting material. The alkyl benzenes suitable for use herein do not generally occur in their natural state and accordingly are mor conveniently prepared by synthesis from more common starting materials, for example, by the Well-known alkylation reaction wherein an olefin-acting aikylating agent, such as an olefinic hydrocarbon containing the requisite 6 to 18 carbon atoms is condensed with benzene, toluene or xylene in the presence of an acidic alkylation catalyst (such as concentrated sulfuric acid, anhydrous aluminum chloride, liquefied hydrogen chloride, etc.) at specific, well-known alkylating or condensation reaction conditions to form the mono-long-chain alkyl-substituted benzene hydrocarbon. In order to provide an alkyl cyclic hydrocarbon having sufiicient hydrophobic properties to produce a surface active agent as the ultimate product in the present synthesis, the long-chain alkyl group substituted on the cyclic hydrocarbon nucleus must contain at least 6, up to about 18, and more preferably, from about 9 to about 15 carbon atoms. Accordingly, in the alkylation of the cyclic hydrocarbon, such as benzene, toluene, or xylene, the olefin-acting alkylating agent must contain a similar number of carbon atoms in order to result in the substitution of an alkyl group having the desired chain length on the benzene ring.

When employing a total synthesis as the most readily available derivation of the starting materials for the production of the present compounds, the next step in the total synthesis is the mono-substitution of an acetyl group on the alkyl cyclic hydrocarbon ring to thereby form an alkyl acetophenone and this synthesis may be readily accomplished by the well-known acetylation method, comprising, for example, the reaction of an acetylating agent, such as acetyl chloride or acetic anhydride with the alkyl benzene hydrocarbon, preferably catalyzed with a suitable condensation catalyst, such as aluminum chloride, forming an alkyl acetophenone product. By virtue of the activating action of the long-chain alkyl group on the benzene nucleus and by virtue, further, of the activating efiect of the carbonyl radical adjacent to the omega methyl group in the resulting acetyl radical, the hydrogen substituents on the omega carbon atcm of the acetyl group condense with from 1 to3 ROH It will be noted that the products resulting from the condensation of acetophenone with formaldehyde contain from 1 to 3 methylol groups on the omega carbon atom of the acetophenone starting compound (marked in the above equations by an the resulting methylol radicals containing hydroxyl groups which may be condensed with an alkylene oxide or glycidol to form from 1 to 3 poly- (oxyalkylene) chains. In addition to the above methylolsubstituted derivatives utilized as intermediates in the condensation reaction, the intermediate products maybe subjected to mild hydrogenation in order to convert the carbonyl group to an hydroxyl radical which is also condensable with an alkylene oxide or glycidol to form still another poly-(oxyalkylene) chain, as hereinafter described.

The aldol-type condensation reaction involving the reaction of formaldehyde with the alkyl acetophenone intermediate utilizing from 1:1 to 3:1 or more molar proportions of formaldehyde to ketone is catalyzed with a basic catalyst present in the reaction mixture. Typical catalysts suitable for this reaction include such bases as the alkali metal and alkaline earth metal hydroxides (preferably potassium or sodium hydroxide, but also including lithium hydroxide, calcium hydroxide, magnesium hydroxide, and barium hydroxide), a basic amine, such as an alkyl ammonium hydroxide or a heterocyclic, basic nitrogen compound such as pyridine. The presence of even small amounts of the basic catalyst (generally from 1 percent to about 10 percent by weight of the ketone) in the reaction mixture initiates the reaction at room temperature and results in an almost quantitative yield of the omega-methylol-substituted intermediate.

The characterization of the hydrophobic group as a long-chain alkyl-substituted cyclic hydrocarbon nucleus is intended to include not only the C (i.e., monocyclic) benzene derivatives, including longchain alkyl substituted toluene and Xylene derivatives, but also the corresponding naphthenes formed by hydrogenation of the aryl nucleus of the intermediate derivatives following the condensation of the alkylacetophenone with formaldehyde. Thus, the alkyl acetophenone condensation product with formaldehyde may be subjected to hydrogenation to convert not only the carbonyl group to a methylol radical, but also at hydrogenation conditions sufficiently severe to saturate the aromatic nucleus, forming the correspond-- ing alkyl-substituted cyclohexane derivative. It is also feasible to saturate the aromatic nucleus at any reaction stage following the condensation of the oxyalkylating agent withthe intermediate methylol-substituted acetophenone, particularly if the retention of an hydroxyl radical, rather than a poly-(oxyalkylene) chain on the carbon atom adjacent to the cyclic hydrocarbon ring alkylation reaction.

is desired. In the latter instance the condensation of the methylol-substituted acetophenone with the oxyalkylatin'g agent is effected prior to the hydrogenation reaction, such that the intermediate reactant entering the oxyalkylation reaction contains a non-reactive carbonyl group, rather than an inter-condensable hydroxymethylene group in the position adjacent to the cyclic hydrocarbon ring. In the event, however, that an additional hydrophilic radical condensable with an oxyalkylating agent is desired in the formation of the ultimate product, thereby increasing the ultimate water-solubility of the condensation product, the intermediate meLhylol ketone may be subjected to hydrogenation to reduce the carbonyl group to an hydroxymethylene radical and the resultant product containing an additional hydroxyl group charged to the oxyalkylation reaction. During such hydrogenation of the carbonyl group, the reaction conditions may be adjusted, for example, by increasing the pressure and/or temperature, to effect simultaneous reduction of the aryl nucleus of the intermediate, particularly if a product having greater stability (e.g. resistant to oxidative deterioration) and/or higher melting point is desired. Such intermediate hydrogenation is generally accomplished catalytically by contacting the intermediate in the presence of hydrogen with a hydrogenation catalyst, such as nickel, cobalt or nickel-cobalt deposited upon a kieselguhr support, platinum or palladium deposited upon alumina, or other well-known hydrogenation catalyst. Thus, hydrogenation of the keto carbonyl group may be effected at relatively mild conditions, such as at temperatures of from about 25 C. to about 150 C. and at hydrogen pressures of from about 5 atmospheres to about 100 atmospheres. If simultaneous reduction of the C ring is desired, temperatures of from about 80 to about 250 C. and slightly higher pressures, generally, from about 10 to about 100 atmospheres are preferable.

In the oxyalkylation of the intermediate monoor polyhydric alcohols, the oxyalkylating agent is selected from ethylene oxide, propylene oxide, glycidol, or mixtures thereof, the condensation thereby introducing one or more hydrophilic poly-(oxyalkylene) chains into the intermediate alkanol to form the surface active product of this invention.

The oxyalkylation reaction is preferably effected in the presence of a catalytic agent, generally selected from the organic and inorganic alkaline compounds. Suitable reaction conditions for the catalyzed process include reaction temperatures generally above room temperature, up to about 150 C., and more preferably within the range of from about 50 to about 120 C. and superatmospheric pressures, preferably above about 10 to about 500 lbs./in. Of the inorganic, basic catalysts for this stage of the process, the alkali metal hydroxide, such as sodium hydroxide and potassium hydroxide, preferably in powdered, anhydrous form, are preferred, the reaction being effected under substantially anhydrous conditions. The alkali metals may be combined with certain organic radicals, as for example, in the form of an alkali metal alkoxide, such as sodium methylate, sodium ethylate, lithium methylate,-potassium methylate and other alkoxides of higher alcohols, the alkali metal alkoxides of the lower alcohols constituting one of the preferred catalysts for the present oxyalkylation reaction. Certain alkali metal salts of weak acids, such as the formates, acetates and propionates also act catalytically in the oxy- A particularly preferred class of catalysts for promoting the condensation reaction are the organic nitrogen bases, such as pyridine, trimethylamine, trimethylammonium hydroxide, etc.; these are of organic composition and thus may be left in the crude detergent product, if desired. The quantity of catalyst generally found to be suitable for promoting the oxyalkylation reaction is an amount sufficient to provide from about oneetenth to about two moi percentcatalyst,

,eral, determines the hydrophobicity of the alkyl cyclic hydrocarbon group), the number of oxyalkylene units required to form one or more hydrophilic oxyalkylene chains of sufficient hydrophilic activity to balance the effect of the hydrophobic group when put into solution is variable, the total number of oxyalkylene units introduced into the product being within the broad range of from about 6 to about 30. The actual number of oxyalkylene units required in any given instance also depends upon the number of methylol (that is, hydrophilic hydroxyl groups) present in the intermediate subjected to the oxyalkylation reaction and also upon the specific oxyalkylating reagent utilized; that is, whether ethylene oxide, propylene oxide, glycidol or mixtures thereof is charged to the oxyalkylation reaction. Thus, fewer oxy ethylene units will be required to form a surface active product than will be required when utilizing propylene oxide or mixtures of ethylene and propylene oxides. Because of the presence of an additional hydrophilic radical in glycidol, substantially less of the latter reagent will be required than in the case of either ethylene oxide or propylene oxide.

It is not known conclusively whether the oxyalkylene units introduced during the condensation reaction become distributed in more than one poly-(oxyalkylene) chain or add to the w-hydroxyalkyl group at the end of a chain once started (i.e., whether the alkylene oxide reactant preferably condenses with a previously condensed alkylene oxide unit to form a single, long poly-(oxyalkylene) chain or whether the reacting alkylene oxide preferentially reacts initially with the l to 4 hydroxyl radicals available in the alkanol intermediate to form several shorter polyoxyalkylene chains). Thus, although it is known that the oxyalkylation product contains from about 6 to about 30 total average number of oxyalkylene units per molecule, it is not definitely determinable whether the oxyalkylene units are distributed in one poly-(oxyalkylene) chain containing from 6 to about 30 units, in two chains containing from 3 to about 15 units, in three chains each containing from 2 to about 10 units (or in one chain containing from 4 to 20, plus two chains each containing from 1 to 5 units), or whether a more random distribution of the oxyalkylene units prevails'. Accordingly, the products of this invention are defined structurally by the method of their preparation, rather than by a structural formula which would attempt to assign a definite structure to the products of the condensation reaction. It is known that different individual molecules present in the mixture of products formed by the oxyalkylation reaction contain varying proportions of alkylene oxide units in the structure of the compounds and in some instances the number of alkylene oxide units in indi idual molecules may vary from 1 to 30, or more, not necessarily being equally distributed between different molecules. Accordingly, the number of oxyalkylene units herein designated for the present products must necessarily refer to an average for the various compounds comprising the mixture obtained from the reaction. For most purposes the most highly effective surface active products contain an average of from 6 to about 10 oxyalkylene units when the alkyl radical attached to the cyclic hydrocarbon ring contains from 6 to about 9 carbon atoms; from about 10 to about 18 oxyalkylcne units when the alkyl group attached to the cyclic hydrocarbon ring contains from 9 to 12 carbon atoms; from about 12 to 20 oxyalkylene units when the alkyl radical attached to the cyclic hydrocarbon ring contains from 12 to 15 carbon atoms; and from about 18 to about 30 oxyalkylene units when the alkyl radical attached to the cyclic hydrocarbon nucleus contains from 15 to 18 carbon atoms. The number of oxyalkylene units required to produce surface active products also varies in accordance with the type of oxynlkylating agent utilized, that is whether ethylene oxide, glycidol or propylene oxide or a mixture thereof is employed in the oxyalkylation process. In general, fewer oxyalkylene radicals are required to produce a surface active agent when utilizing glycidol than ethylene oxide, because of the greater water-solubilizing (more highly hydrophilic) capacity of an hydroxyl-bearing ethylene oxide molecule; stated otherwise, products containing the same number of oxypropylol groups (derived from glycidol) as oxyethylcne units are more soluble in water.

The term oxyalkylene and oxyalkylating agent is intended to include by definition the oxypropylol or methyloloxyethylene radical introduced into the condensation product by reacting the mega-methylol-substituted alkyl acetophenone derivative with glycidol, as well as the groups introduced by condensing the intermediate with ethylene oxide, propylene oxide or mixtures thereof, the reaction, in any event, introducing oxyalkylene units into the intermediate condensation product.

The products of this invention exist in the form of viscous liquids or solid, waxlike materials, depending upon the number of oxyalkylene units present in the product, as well as the size of the nuclear alkyl substituent. The melting points and viscosity of the products also increase as the number of alkylene oxide units present in the product increases.

The present invention is further illustrated with respect to several of its specific embodiments relating to particular charging stocks, methods of operation and process conditions in the following examples which, however, are not intended to restrict the scope of the invention necessarily in accordance therewith.

Example I Nuclearly-substituted dodecylacetophenone is prepared by the acetylation of dodecylbenzene which is formed in a preliminary reaction by the alkylation of benzene with an olefinic fraction containing C monoolefins (a propylene tetramer fraction boiling from 170 to about 225 C.), in accordance with well-known alkylation procedures. Acetylation of dodecylbenzene readily effected by condensing acetyl chloride with dodecylbenzene in the presence of anhydrous, powdered aluminum chloride by well-known acetylation procedures.

The dodecylacetophenone prepared as indicated above is converted to the trimethylol derivative thereof by an aldol-type condensation reaction with formaldehyde, the latter reaction being eilected by mixing 6 molar pro portions of formaldehyde (as a 30% aqueous solution of formalin) with the previously prepared dodecylacetophenone, adding to the resulting mixture, with stirring, a quantity of 30% aqueous sodium hydroxide solution corresponding to by weight of the dodecylacetophenone. The mixture is rapidly stirred as the caustic is added to the acetophenone-formaldehyde mixture, the temperature of the mixture being maintained as closely as possible at approximately 30 (1. As the condensation proceeds, the two-phase reaction mixture gradually becomes turbid and milky, indicating that the reaction product emulsifies with water as the condensation pro ceeds. A 90% recovery of the desired trimethylol-substituted acetophenone is elfected by salting out the desired product from the aqueous solution with sodium sulfate added to the aqueous solution until saturated. The remaining trimethylol derivative is recovered by extraction of the aqueous solution with diethyl ether. A carbonhydrogcn-oxygen analysis of the recovered product indicates that a trimethylol-substituted acetophenone is obtained as the product of the above reactions.

The product prepared as indicated above is a viscous, clear liquid which is soluble in water to the extent of 0.6 part per parts of water at 25 C. and forms an aqueous solution which readily foams when shaken. In order to determine its surface active properties, a 0.3% aqueous solution of the product is prepared and tested for detergenc'y in accordance with the standard Launder- O-Meter procedure. For this purpose, soiled swatches of cotton 'muslin are laundered in the 0.3% aqueous solution of the trimethylol product at F. and the reflectance of the resulting laundered cotton swatch compared with the reflectance of a similarly prepared cotton swatch laundered in a 0.3% aqueous solution of sodium dodecylbenzene sulfonate, laundered in accordance with the same procedure, under similar test conditions. A comparison of the reflectance of white light by photoelectric means from the cotton swatches indicates that the omega-trimethylol-substituted acetophenone has a detergency equivalent to approximately 40% that of dodecylbenzene sulfonate.

The omega-trimethylol dodecylacetophenone product prepared as indicated above is converted to a more active detergent and a more water-soluble product by subjecting the same to mild hydrogenation, in the presence of a hydrogenation catalyst comprising nickel supported on kieselguhr su'hicient to reduce the keto oxygen atom to an hydroxyl group but insufiicient to hydrogenate the aromatic nucleus, in accordance with the following procedure: A 0.3 mole aliquot of the above product is dissolved in 10 volumes of 95% ethanol and charged, together with 10% by weight of the ltetone of an 8% nickel 0n ltieselguhr catalyst, into a rotating pressure autoclave. Hydrogen is thereafter charged into the autoclave to a pressure of 10 atmospheres, and the mixture is allowed to react heating at 50 C. for three hours while the autoclave is slowly rotated; a determination of the acetyl number for the product indicates that it contains about 4 hydroxy groups per molecule. A detergency test on the product (0.3% aqueous solution, compared to a 0.3% aqueous solution of sodium dodecylbenzene sulfonate) indicates that its detergency is approximately 58% of sodium dodecylbenzene sulfonate.

The detergency and water solubility of the trimethylolsubstituted acetophenone intermediate formed as indicated above is substantially enhanced by further condensing it with ethylene oxide or glycidol to thereby increase the size of the hydrophilic portion of' the molecule and increase its water solubility. The trimethylolsubstituted dodecylacetophenone is condensed first with 2 molar proportions of ethylene oxide, a sample taken of the condensation product, and the product of the reaction thereafter successively reacted With additional 4 molar aliquots of ethylene oxide, with intermediate sampling, until approximately 30 moles of ethylene oxide has been reacted with the trimethylol-substituted dodecylacetophenone. Each of the intermediate samples is tested for detergency in accordance with the above-described standard Launder-O-Meter procedure by comparison with an aqueous solution of sodium dodecylbenzene sulfonate of equal concentration and under equal test conditions.

The initial condensation reaction with 2 moles of ethylene oxide is effected by adding to the trimethylol-substituted dodecylacetophenone about 0.5% of its Weight of powdered, dry sodium hydroxide, heating the mixture to about 90 C. and then gradually charging 2 molar proportions of ethylene oxide to the mixture with continuous stirring. The reaction is stirred and maintained at 90 C. during the addition and for an hour thereafter. Following the removal of a sample of the condensation product, an additional 4 molar proportions of ethylene oxide is gradually charged to the reaction mixture and the reaction at the above-indicated conditions repeated. In detergency tests run on samples of each of the resulting condensation products, the detergency rating (in comparison with sodium dodecylbenzene sulfonate at equivalent concentrations determined in accordance with the standard Launder-O-Meter procedure) increases to 148% when the product contains a total average of about 14 oxyethylene units and gradually decreases to 70% for the product containing a total of about 39 oxyethylene units per molecule.

Example II As hereinabove described, the trimethylol-substituted dodecylacetophenone can be hydrogenated to produce a product containing an additional hydroxyl group on the carbon atom alpha to the phenyl ring. This tetrahydroxy intermediate was reacted with successive portions of ethylene oxide and the detergency of the products was compared to the corresponding derivatives of the parent trimethylol dodecylacetophenone. It was found that the elfect of the additional hydroxyl radical in the structure of the compound is sufficient to reduce the number of moles of ethylene oxide required to form a product of equivalent detergency by approximately 2 moles per mole of intermediate.

Utilizing a series of alkyl-acetophenones (hexyl-acetophenone, nonyl-acetophenone, pentadecyl-acetophenone and octadecyl-acetophenone which were the propylene polymer alkylates of acetophenone) as initial starting materials and in each case converting these alkylates to their trimethylol-substituted derivatives by an aldol-type condensation reaction similar to the procedure described in Example I, followed by oxyalkylating the resulting trimethylol derivatives, it is found that as the average number of ethylene oxide units in the resulting condensation product increases up to about 34, the detergency of the resulting ethylene oxide condensation products increases and passes through a maximum, for each alkyl-acetophenone derivative, the number of ethylene oxide units per molecule required for maximum detergency for each of the various alkyl-acetophenones varying with the number of carbon atoms in the alkyl group; the maximum detergency developed in each series of compounds, however, was somewhat less than the maximum detergency of the oxyethylated dodecylacetophenone.

Example Ill Dodecylacetophenone, prepared as indicated above, converted to its trimethylol-substituted derivative by condensation with formaldehyde and reacted with glycidol at C. in a reaction catalyzed with 1% by weight of pyridine, based on the dodecylacetophenone charged, yielded detergent products of equivalent detergency at much lower glycidol to dodecylacetophenone ratios than ethylene oxide to dodecylactophenone in the latter type of condensates. A product having greater water solubility and approximately the same detergency as the product containing an average of about 14 ethylene oxide units is obtained when the average number of glycidol units per molecule is about 8.

I claim as my invention:

1. An oxyalkylated omega-methylol-substituted alkylacetophenone having from 6 to about 18 carbon atoms in the alkyl group and having from 1 to 3 oxyalkylated methylol groups on the omega carbon atom of the acetophenone, said oxyalkylated compound containing from about 6 to about 30 total average number of oxyalkylene units derived from an oxyalkylating agent selected from the group consisting of ethylene oxide, glycidol, propylene oxide and mixtures thereof.

2. An oxyalkylated mono-omega-methylol-substituted alkyl-acetophenone having from 6 to about 18 carbon atoms in the alkyl group and containing from about 6 to about 30 total average number of oxyethylene units on the methylol group.

3. An oxyalkylated tri-omega-methylol-substituted a1- kyl-acetophenone having from 6 to about 18 carbon atoms in the alkyl group and containing from about 6 to about 30 total average number of oxyethylene units on the methylol groups.

4. Oxyethylated omega-trimethylol dodecylacetophenone containing from about 6 to about 30 total average number of oxyethylene units on the methylol groups.

References Cited in the file of this patent UNITED STATES PATENTS 2,207,612 Coleman et a1. July 9, 1940 2,596,093 Benneville May 13, 1952 2,768,956 Scott Oct. 30, 1956 

1. AN OXYALKYLATED OMEGA-METHYLOL-SUBSTITUTED ALKYLACETOPHENONE HAVING FROM 6 TO ABOUT 18 CARBON ATOMS IN THE ALKYL GROUP AND HAVING FROM 1 TO 3 OXYALKYLATED METHYLOL GROUPS ON THE OMEGA CARBON ATOM OF THE ACETOPHENONE, SAID OXYALKYLATED COMPOUND CONTAINING FROM ABOUT 6 TO ABOUT 30 TOTAL AVERAGE NUMBER OF OXYALKYLENE UNITS DERIVED FROM AN OXYALKYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF ETHYLENE OXIDE, GLYCIDOL, PROPYLENE OXIDE AND MIXTURES THEREOF. 